CN1198787C - Continuous hydrogenation process of aromatic nitro-compound using low content of aluminium catalyst - Google Patents
Continuous hydrogenation process of aromatic nitro-compound using low content of aluminium catalyst Download PDFInfo
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- CN1198787C CN1198787C CNB011178582A CN01117858A CN1198787C CN 1198787 C CN1198787 C CN 1198787C CN B011178582 A CNB011178582 A CN B011178582A CN 01117858 A CN01117858 A CN 01117858A CN 1198787 C CN1198787 C CN 1198787C
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 51
- -1 aromatic nitro-compound Chemical class 0.000 title claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 239000004411 aluminium Substances 0.000 title claims description 48
- 239000003054 catalyst Substances 0.000 title abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 230000002093 peripheral effect Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 229910045601 alloy Inorganic materials 0.000 claims description 24
- 239000000956 alloy Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000002019 doping agent Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002828 nitro derivatives Chemical class 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000000373 fatty alcohol group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 description 21
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007868 Raney catalyst Substances 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009795 derivation Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BSMKYQUHXQAVKG-UHFFFAOYSA-N 1-nitro-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1[N+]([O-])=O BSMKYQUHXQAVKG-UHFFFAOYSA-N 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for the hydrogenation of nitro-aromatic compounds comprises a reactor zone, a separation zone and peripherals, the hydrogenation process is continuous and uses a catalyst comprising nickel and, optionally, aluminum; if present, the Al content is no greater than 5.5% of the total catalyst and the dwell time of the catalyst in the reactor zone, separation zone and peripherals is at least 3 days. The invention also included for the use of the catalyst in the process for the hydrogenation of nitro-aromatic compounds with the aim of limiting the formation of nickel aluminates, the catalyst comprises nickel and, optionally, aluminum; if present, the Al content is no greater than 5.5% of the total catalyst.
Description
Theme of the present invention is that a kind of low content of aluminium catalyst that uses carries out the method for shortening continuously to aromatic nitro compound, and the condition of carrying out hydrogenation should make the residence time of catalyzer be at least 3 days.
For many years, the catalytic hydrogenation method of aromatic nitro compound has been known.Generally speaking, these methods generally include two districts and peripherals, and first district is the zone that actual hydrogenation reaction is carried out.Second district is the zone of separating catalyst from reaction mixture.Peripherals refer to be used for to carry the pipeline of reaction mixture and/or reactant and equipment (basin, circulation tank, pump, etc.) and be used for one or more districts of preparation feedback mixture.Should be noted that the nitro-compound, fresh solvent (if use), live catalyst and the catalyst suspension that come from reaction zone and disengaging zone subsequently are generally mixed in this preparation district.With reaction and disengaging zone separately is unnecessary, and this is because they can exist in same device, as for example when the use reactor/slurry tank.Hydrogenation reaction is the reaction of the very fast and strong heat release of a kind of reaction, and it carries out in stirred reactor or annular-pipe reactor usually.Separating the method come from hydrotreated catalyzer can carry out in every way, as tangential flow filtration, laterally filter and precipitate.
Usually, the method for hydrotreating of aromatic nitro compound is to use the catalyzer that comprises nickel and aluminium at least to carry out.Often the catalyzer that uses is the raney nickel type catalyzer.This catalyzer can mix up various metals, for example iron and/or chromium.These catalyzer are by to comprising catalyst metal, carry out as the alloy of nickel, aluminium and possible one or more dopant metals that alkaline purification obtains.
By convention, utilize in the commercial run of Raney catalyst exploitation, residual aluminium content is than higher, and the weight in catalyzer is approximately 7-15%.
In the present invention, do not query the advantage of above-mentioned catalyzer, find that just these catalyzer have several shortcomings, when promptly using these catalyzer under the condition of reacting continuously, the residence time of catalyzer is very long.If when under the condition of high productive capacity, using these catalyzer, have identical limitation.
This is because under these conditions, the derivation oxidation that is present in the nickel in the catalyzer becomes very big.Along with the prolongation of time, on the wall of above-mentioned reactor, slurry tank and/or peripherals, form a kind of extremely hard throw out.The present invention has confirmed that this throw out has the nickel aluminate structure, and for example a kind of lamellated double-hydroxide of takovite type, this throw out are because the existence of the aqueous alumina of the derivation oxidation of this significant nickel and association generates.
This throw out generates one deck screen-wall on the wall of reactor, setting tank and peripherals, thereby has reduced the throughput of this method, and in fact, wants that the target that reaches is to increase throughput.
Therefore,, close equipment or the district discussed, and be essential its cleaning with the quite approaching regular timed interval.Yet this operation is very tedious, and bigger equipment is removed this throw out because it need use yield-to-weight ratio, as using High Pressure Gun.
Therefore, the objective of the invention is to eliminate this shortcoming, or reduce its nonconforming influence at least very bigly.
Thereby, theme of the present invention is a kind of catalytic hydrogenation method of aromatic nitro compound, comprise a reaction zone, disengaging zone and peripherals, in the method, use to comprise nickel at least and may wrap aluminiferous catalyzer, if make hydrogenation carry out existing aluminium continuously, the total aluminium content in catalyzer is at most 5.5% in the weight of this catalyzer, and the residence time of this catalyzer in reaction zone, disengaging zone and peripherals was at least three days.
Term " total aluminium " is understood that aluminium (O) and aluminium (+III) sum.
Have now found that, with regard to commercial production scale, by carrying out hydrogenation under these conditions, with content by directly beginning just to use a kind of total aluminium content to exist well below plant-scale catalyzer of having developed from hydrogenation reaction, perhaps even use a kind of not aluminiferous in some cases catalyzer, the generation of nickel aluminate is greatly slowed down, perhaps even be eliminated.
Therefore, second theme of the present invention is the purposes that comprises nickel at least and may wrap aluminiferous catalyzer, if there is aluminium, when carrying out the catalytic hydrogenation reaction of aromatic nitro compound continuously, in order to limit the generation of nickel aluminate, total aluminium content by weight is at most 5.5%.
Reducing the generation of (or restriction) nickel aluminate especially can preferably increase by 2 times and see at least by the operating time of this method between twice parking increased by 1.5 times at least.Should remember that this twice parking is necessary, because the nickel aluminate throw out has hindered the normal running (reduction of throughput, particularly line clogging) of equipment.Should be noted that when the quantity of initial aluminum in the catalyzer was hanged down, maybe when not having aluminium, it was possible not stopping between two operating times of regulation.
In addition, surprisingly, the use of this catalyzer can not reduce the productive rate and the consumption of the performance, particularly catalyzer of reaction significantly.Even more noteworthy, use such catalyzer can help to improve the performance of reaction.
As an explanation, under condition of the present invention, use present method, making the productive rate that adds hydrogen compound (as aromatic amine) reach 99.5% by weight at least becomes possibility.
The catalyzer of Shi Yonging is particularly suitable for realizing per hour transforming the so high productivity of 2 moles of hydrogen with every gram catalyzer in the method, or even transforms 3 moles of hydrogen up to every gram catalyzer per hour.More specifically, press the productive rate of method acquisition of the present invention per hour between every gram catalyzer conversion 0.1 and 3 moles of hydrogen, preferably per hour between every gram catalyzer conversion 0.2 and 2 moles of hydrogen.
In addition, according to method of the present invention, can in this reaction, use nickeliferous catalyzer, for example from other method of hydrotreating, what comprise nitro functions or nitrile adds the employed catalyzer of hydrogen compound, or even from the employed regenerated catalyst of Same Way.
At last, have found that, by the employed catalyzer of method of the present invention even under large-duty condition, slower than those catalyst deactivations commonly used under similarity condition.This is because the hole that has than the catalyzer of low-aluminum-content stops up slower.
Yet, other features and advantages of the present invention below having read explanation and embodiment after will become clearer.
As mentioned above, method of the present invention relates to the method for hydrotreating of aromatic nitro compound in the presence of the catalyzer of nickeliferous and aluminium.
According to a feature of the present invention, total aluminium content that catalyzer contains is at most 5.5% in the weight of catalyzer, should be noted that, this catalyzer has maximum initial aluminum content, that is to say aluminium content maximum before carrying out hydrogenation reaction.
According to realizing first concrete grammar of the present invention, total aluminium content is by weight more than or equal to 1% of total catalyst weight.
Preferably, total aluminium content by weight total catalyst weight 1% to 5.5% between.More preferably, total aluminium content by weight total catalyst weight 2% to 5% between.
According to first derived method of realizing first method of the present invention, this catalyzer is to obtain from a kind of alloy based on nickel, aluminium and at least a possibly dopant (raney alloy).
In the dopant that this area is used always, what can mention is to be prepared by the metal in IVA, VA in the periodic table of elements (the ChemicalSociety of France Bulletin No.1, January 1966, appendix), VIA, the VIII family.Preferably, dopant is selected from titanium, iron and chromium or their mixture.
Such catalyzer can obtain from various sources.
According to first kind of possible source, can use a kind ofly from a kind of aluminium, nickel and catalyzer of the alkaline purification of the alloy of at least a dopant possibly of comprising, the characteristic of this alloy and/or the condition of making the condition of this alloy and/or carrying out alkaline purification make total aluminium content be no more than 5.5% in catalyst weight.
Alkaline purification can advantageously be carried out as follows.
At first, alkali cpd generally is a kind of basic metal, as the oxyhydroxide of lithium, sodium, potassium, caesium and rubidium.
For example, this processing can be carried out with basic cpd excessive with respect to aluminium.More specifically, said basic cpd can use with the amount of mol ratio between 1.5 to 10 of the mole number of a kind of basic cpd and the aluminium that exists.Preferably, said ratio is between 1.5 to 3.
In addition, be to use basic cpd traditionally with the form of the aqueous solution.More specifically, when beginning to handle, between 10% to 50%, preferably, said concentration is by weight between 15% to 30% by weight for the concentration of alkali cpd.
For favourable and safe reason, alkaline purification is to carry out below the hydrogen content in gas phase remains on the limits of explosion of air/hydrogen gas mixture.
For example, this condition can be passed through at air or a kind of rare gas element, as, especially carry out said processing under the air-flow of nitrogen and obtain.
Also it should be noted that, more specifically, carry out the saturated vapour pressure of the pressure of alkaline purification more than or equal to the liquid medium under the temperature of alkaline purification.
The inventor reminds the reader to note, this liquid medium comprises, particularly, and water, dissolved aluminium salt and basic cpd.
In addition, term " saturated vapour pressure " is illustrated in the dividing potential drop of liquid medium under the temperature of being discussed.
In addition, preferably between 50 ℃ to 130 ℃, more advantageously, said processing is under the temperature between 60 ℃ to 90 ℃ for the temperature of carrying out alkaline purification.
The temperature that is noted that processing can change in the alkaline purification process.More specifically, it will be favourable increasing the temperature of handling end.
About the time length of alkaline purification, more particularly between 1 to 12 hour.Usually the time length is between 1 to 3 hour.
At last, it should be noted that above-mentioned condition selects by this way, that is, make aluminium keep a kind of soluble form,, in the alkaline purification process, can after processing, from remaining solid, separate particularly as a kind of aluminate.
First kind of possibility is, uses a kind of catalyst precursor alloy with high aluminium content.For example, a kind of aluminium content can be suitable for the present invention in the weight of alloy greater than 50% alloy.
More specifically, this alloy tool is less than in the weight of alloy or equals 70% aluminium content, is preferably weight in alloy between 55 to 70%.The inventor should point out that use aluminium content can not exceed scope of the present invention greater than 70% alloy yet.But, use such alloy in treating processes, may produce unnecessary extra-expense (cost of starting material (alkali cpd) and the processing costs of effluent).
According to a kind of favorable method of realizing this first kind of possible method, if and a kind of dopant is present in the precursor alloy, preferably a kind of dopant content is no more than 5% in weight alloy, more preferably is no more than 3% alloy and handles in weight alloy.
Second kind of possibility be, the alkaline purification of precursor alloy is to carry out under than the above-described higher levels of condition represented with respect to alkaline purification a kind of.Therefore, in above-mentioned condition, all requirements are to have at least a condition to be in higher level, carry out so that processing is regarded as on higher level.For example, these conditions can be by a kind of higher basic cpd/aluminium (Al) mol ratio, and/or a kind of starting point concentration of higher basic cpd, and/or a kind ofly in treating processes or at the end for the treatment of processes, keep higher temperature, and/or a kind of long time length is formed.
According to a kind of concrete grammar of realizing second kind of possibility, it also is possible carrying out a kind of extra alkaline purification, that is to say that the product that first kind of alkaline purification from alloy obtained carries out at least a other alkaline purification, so that further reduce remaining aluminium content.
Therefore, can expect, under the condition of routine, carry out first kind of alkaline purification, and under aforesaid higher levels of condition, carry out second kind of alkaline purification.
Equally, it is possible carrying out second kind of alkaline purification under the condition of similar first kind of processing.
The third possibility is, uses a kind of catalyzer from alloy, process particular processing in the manufacturing processed of alloy.Therefore, using a kind of is possible by the resulting catalyzer of the annealed step of alloy.
More specifically, according to the third possibility, alloy pig is being lower than under the temperature of peritectic temperature through heat-treated, and the result generates NiAl
3More specifically, the temperature of using in thermal treatment is between 650 ℃ and 850 ℃
This processing is advantageously carried out in an inert atmosphere.
The structure of alloy is reset in this processing, and promotes the generation of rich aluminium phase, for example, and NiAl
3Or eutectic phase.Yet,, in the alkaline purification process, can easily remove these aluminium in mutually in order to obtain actual catalyst.
Certainly, the combination of using above-mentioned three kinds of possibilities can not exceed scope of the present invention.
The another kind of possible source of catalyzer is from used regenerated catalyst in the hydrogenation process, this hydrogenation process can with wherein used the different of this catalyzer, also can be identical.
As an illustration, in the hydrogenation process that comprises nitro functions or nitrile compounds, use mix up or the non-raney nickel type catalyzer that mixes up can be suitable for this derived method.The consumption of catalyzer especially causes remaining aluminium content to reduce significantly in this hydrogenation process.
Before using method of the present invention, water carries out first cleaning operation to catalyzer, and to remove the organic compound of any trace that occurs in the process in front, this is very favourable.Then, the regeneration step that the catalyzer that obtains is comprised at least alkali cleaning operation.The purpose of this operation is to remove all or part of aluminum oxide that exists in the catalyzer.
The detailed conditions of above-mentioned alkaline purification can be used for such cleaning.
Yet,, be to carry out being less than or equal under 150 ℃ the temperature although that depend on the employed equipment and the available energy and imagination adopts higher temperature, said alkali cleaning according to a kind of favorable method of realizing this derived method.More specifically, temperature in or equal 50 ℃, preferably between 80 ℃ and 140 ℃.
According to the characteristic of equipment used, alkali cleaning can be carried out under normal atmosphere or higher pressure.It should be noted that at stagnation pressure greater than 30 * 10
5Handle during Pa and there is no remarkable advantage.
For this basic cpd, in water, can be less than or equal to 35% concentration by weight and use.
Regeneration step also can be advantageously carried out having under the hydrogen pressure that can further reduce nickel oxide.
In this case, more specifically, this processing is to be at least 10 at hydrogen partial pressure
5Carry out under the Pa (1bar).According to employed device, the dividing potential drop of hydrogen can be high as much as possible.Yet hydrogen partial pressure preferably is less than or equal to 30 * 10
5Pa (30bar), when handling with hydrogen, total pressure is preferably 6 and 30 * 10
5Between the Pa (6-30bar).
Realize that second derived method of first method of the present invention is made up of catalyzer and a kind of carrier that use comprises nickel and aluminium.
Nickel also can belong to IVA, VA, VIA, the VIII family element of the periodic table of elements as those in conjunction with at least a metal that mixes up, preferred titanium, iron or chromium or their mixture.
A kind of more specifically material stable under this reaction conditions of the selection of said carrier.
More specifically, carrier comprises and selected among zirconium, titanium and silicon oxide, they itself or their aluminium form of aluminum oxide (more particularly with) of at least a oxide-bonded of mixture.
Should be noted that this catalyzer, no matter its degree of oxidation how, total all will make the aluminium content of this catalyzer can satisfy top specified condition, promptly is no more than 5.5% in total catalyst weight.
More specifically, the amount of carrier in the weight of catalyzer between 25 and 80%, preferably in the weight of catalyzer between 30 and 65%.
Such catalyzer is obtained by a kind of nickel salt of precipitation and at least a possibly salt that mixes up metal on carrier usually.Catalyzer is separated then, for example, by filtering, subsequent drying and at sufficiently high temperature lower calcination so that nickel hydroxide and possible salt that mixes up metal or oxyhydroxide are converted into oxide compound.This step is handled catalyzer after carrying out at once, and during handling, some nickel are reduced.Carry out in the common reducing atmosphere at high temperature of reductive action, as hydrogen.
In reaction of the present invention, use a kind ofly as describing just now, the carried catalyst that once was used in advance in the technology of another kind of hydrogenation is possible.In this case, preferably, before said used catalyst is used to method of the present invention fully, carry out water-washing step, perhaps even the alkali cleaning step, so that remove the organic compound of any trace that previous technology produces.Behind cleaning step, can recommend to reduce processing, carry out in the preferred reducing atmosphere at high temperature, as hydrogen.
According to realizing second concrete grammar of the present invention, catalyzer contains nickel rather than aluminium.
According to this implementation method, employed catalyzer contains a kind of not aluminiferous carrier.Above to the (preparation: source (fresh or regenerated) of aluminiferous carried catalyst, catalytic treatment repeatedly circulated before importing it according to method of hydrotreating of the present invention) explanation done is still effective to realizing this method, and known aluminium can not appear in this concrete implementation method.
Therefore, the catalyzer of mentioning just now is used to comprise in the catalytic hydrogenation reaction of aromatic nitro compound, and carries out continuously.
An important feature of the method according to this invention, the residence time of catalyzer is 3 days at least.
In implication of the present invention, the residence time (T
Res) by as give a definition:
The catalyzer that uses: the amount of reaction zone, disengaging zone and peripherals inner catalyst, represent with kg
The catalyzer that consumes: the amount of the catalyzer of Xiao Haoing (be cleaned, and be not added into the amount of the catalyzer of this process subsequently) in the method; By producing the catalyzer that aminated compound per ton purified, represent with kg
The output of aminated compound: the amount of the aminated compound of production, to represent ton/every day.
Usually, the residence time of catalyzer is about several weeks in these districts.
Particularly, term " aromatic nitro compound " is understood that a kind of compound, and it comprises at least one nitro functions, preferably at least two nitro functions and at least a C
6-C
14, be preferably C
6-C
10The aromatic series unit, above-mentioned aromatic series unit can be by one or more C
1-C
10Straight chain, ring-type or side chain, saturated or unsaturated alkyl and/or one or more hydroxyl replace, and also can not replace.
More specifically, the unitary aforesaid alkyl of said aromatic series may be replaced, C can be selected from
1-C
10, preferred C
1-C
6The group of alkyl, aryl, alkylaryl and arylalkyl.
As the aromatic series unit, can mention phenyl ring and naphthalene nucleus especially, they can be replaced by the group of one or more methyl, ethyl, propyl group, butyl, amyl group or hexyl and/or their isomer, also can not replace.
Method of the present invention can be used and at least aly be selected from single oil of mirbane, dinitrobenzene, MNT, first dinitrotoluene (DNT), the compound in nitrocumene and the o-NP is realized.
The present invention is preferred to be to use a kind of dinitrotoluene (DNT) mixture of isomers.
Aromatic nitro compound can use in the presence of the solvent of said compound.
According to first kind of derived method, the solvent of use is selected from Fatty Alcohol(C12-C14 and C12-C18) or cyclic ethers, their or its mixtures own.
More specifically, methyl alcohol, ethanol, propyl alcohol or Virahol, they itself or its mixture be used as Fatty Alcohol(C12-C14 and C12-C18).
As cyclic ethers, that mentions can be by dioxane and tetrahydrofuran (THF), they itself or its mixture constitute.
According to this derived method, before aromatic nitro compound was imported into reaction zone, they were dissolved into earlier in the mixture of aforesaid solvent or solvent.
The concentration of the nitro-compound in solvent or solvent mixture can change in a wide scope.Yet, can use single-phase mixture, that is,, can use the mixture of the solubility limit that does not reach nitro-compound or composition for solvent of being discussed or mixture.Therefore, do not attempt concentration range is limited in and be less than by weight or equal 25%.
According to second kind of preferred derived method of the present invention, the solvent of use is to add hydrogen compound.If adopt this derived method, aromatic nitro compound is the state importing with liquid or fusing.
The advantage of this derived method is that it is the diluting reaction thing not, comes to this when using the mixture of a kind of solvent or solvent usually.This helps to keep high technology productivity especially.And this derived method has avoided more increasing the step of a product separation from the employed solvent of reaction process, moves the danger that this step has the loss hydrogenated products.
The moment content of nitro-compound in the reaction zone is maintained low as much as possible, measure frequently to guarantee that it can not surpass 1000ppm.By adjusting the feeding rate of nitro-compound, make them once being imported into reactor almost at once by catalyst reduction, keep the content of nitro-compound in the reaction zone.Method of the present invention is very suitable for operating on the high productivity level, that is, aromatic nitro compound is the almost maximum speed feeding being absorbed by reactor/catalyzer.
More particularly, employed hydrogen is pure hydrogen.Term " pure hydrogen " is understood that a kind of gas that contains 99% hydrogen at least, more preferably, contains 99.9% hydrogen at least.Though should be noted that can not provide special benefit to reaction, carries out hydrogenation reaction with the hydrogen that dilutes, and does not exceed scope of the present invention.
Preferably, hydrogen is the amount feeding with stoichiometric ratio.Yet, carry out hydrogenation with the hydrogen that surpasses stoichiometric ratio and also can not exceed scope of the present invention.These conditions favourings more specifically, have been optimized the gas-liquid transmission of some technology in satisfying the hydromechanics standard.
Hydrogen is in 5-70 * 10 in reactor
5It is favourable changing between the Pa (5-70bar), preferably in 10-50 * 10
5Between the Pa (10-50bar).
This gas with the known any method of those skilled in the art this gas imported, so that can distribute in reactor equably.
Preferably, reaction is to carry out in stirred reactor or annular-pipe reactor.
More specifically, temperature is between 50 ℃ to 200 ℃.
After hydrogenation reaction, reaction mixture is separated from catalyzer by precipitation or filtration with usual method.
Certainly, the amount of isolating reaction mixture is corresponding with the amount of nitro-compound, under the situation that solvent exists, is imported into reaction zone, to keep stable operational condition possibly.
Therefore, if reaction is to carry out with solvent, can separate the hydrogenated products that obtain by distillation.Should be noted that the step subsequently that will stand according to choice of Solvent and hydrogenated products, this separating step is not necessary.
Secondly, after the dehydration, the product of this aromatic series hydrogenation can be applied in the phosgenation reaction, and to obtain aromatic isocyanate, it is intermediates of producing urethane, otherwise, if necessary, its distillation is obtained various isomer with separation.
Yet the concrete test that provides does not below limit the present invention.
Embodiment 1
To use two tests (test 1 and test 2), and a kind of nothing that comprises 8% total aluminium by weight of standard be mixed up Raney nickel assess.
A) test 1:
With dinitrotoluene (DNT) (DNT) mixture of isomers of 50 Grams Per Hours, be 150 ℃ in temperature, hydrogen pressure is under the condition of 20bar, import continuously one contain 0.7 the gram Raney nickel reactor in.
The charging of DNT is a successive, and the content of DNT surpasses 1000ppm in reactor.
Import hydrogen according to reaction process.So that in reactor, keep constant voltage.
Afterreaction was terminated in 6 hours.
In the time of t=4 hour, the productive rate of reaction approximately is 99%.
B) test 2:
With the sample (not carrying out hydrogenation as yet) of primary catalyst in tolylene diamine (TDA) mixture of isomers and water import a Glass tubing that is called the Carius pipe, and, under being 150 ℃ and the condition of pressing certainly, temperature deposited one month then its sealing.
After one month, open this pipe; This catalyzer can not be restored, and extremely hard.
With finding behind the X-ray diffraction that the structure of this catalyzer has a kind of nickel aluminate structure (takovite).This structure is identical with the structure of observed throw out (screen-wall) on the wall of plant-scale device.
Embodiment 2
The catalyzer that uses reclaims, comprises by weight the Raney nickel of 3.5% total aluminium from the nitro hydrogenation unit.This catalyzer at first water cleans, and (1N) sodium hydroxide with dilution cleans then, and then water cleans.Then, this catalyzer is assessed in as example 1 described same test method.
A) test 1:
Repeat the test 1 of embodiment 1.
The result is as follows:
Afterreaction was terminated in-8 hours.
-in the time of t=4 hour, the productive rate of reaction is 99.2%.
B) test 2:
Repeat the test 2 of embodiment 1.
The result is as follows:
After-one month, open this pipe, this catalyzer is reducible, and slightly a bit hard.
With finding behind the X-ray diffraction that the structure of this catalyzer is a kind of structure of nickel basically.It contains nickel aluminate than small proportion (being half of nickel aluminate content in the catalyzer of embodiment 1 at least).
Embodiment 3
In this embodiment, the catalyzer of use is that a kind of nothing is mixed up Ni-based carried catalyst, exists with the form of aluminum oxide, contains total aluminium of about 2% by weight, 2 to 6% ZrO
2, silicon oxide and total by weight nickel content is 55% nickel.
Use and this catalyzer is assessed with example 1 described identical test method.
A) test 1:
Repeat the test 1 of embodiment 1.
The result is as follows:
Afterreaction was terminated in-9 hours.
-in the time of t=4 hour, the productive rate of reaction is near 99.2%.
B) test 2:
Repeat the test 2 of embodiment 1.
The result is as follows:
After-one month, open this pipe, this catalyzer is reducible and not hard.
With finding behind the X-ray diffraction that the structure of this catalyzer is viewed the same with live catalyst basically.
Claims (18)
1. the catalytic hydrogenation method that comprises the aromatic nitro compound of at least two nitro functions, this method adopts a reaction zone, disengaging zone and peripherals, it is characterized in that, use a kind of comprise nickel at least and optionally wrap aluminiferous catalyzer hydrogenation is carried out continuously, if there is aluminium to exist, total aluminium content in catalyzer is at most 55% in the weight of this catalyzer, and the residence time of catalyzer in reaction zone, disengaging zone and peripherals was at least 3 days.
2. according to the method for claim 1, it is characterized in that with respect to the weight of catalyzer, total aluminium content is more than or equal to 1%.
3. according to the method for claim 1, it is characterized in that with respect to the weight of catalyzer, total aluminium content is by weight between 2% to 5%.
4. according to the method for one of claim 1-3, it is characterized in that, catalyzer be with a kind of comprise nickel, aluminium and optionally the alloy of at least a dopant obtain.
5. according to the method for claim 4, it is characterized in that dopant is selected from IVA, VA in the periodic table of elements, VIA, VIII family element.
6. according to the method for claim 4, it is characterized in that hotchpotch is selected from titanium, iron and chromium or their mixture.
7. according to the method for one of claim 1-3, it is characterized in that catalyzer comprises a kind of carrier.
8. according to the method for claim 7, it is characterized in that this carrier comprises the oxide compound with selected among zirconium, titanium and silicon, they itself or their aluminum oxide of at least a oxide-bonded of mixture.
9. according to the method for claim 1, it is characterized in that this catalyzer comprises a kind of not aluminiferous carrier.
10. according to the method for one of claim 1-3, it is characterized in that hydrogenation is to carry out under the temperature between 50 to 200 ℃.
11. the method according to one of claim 1-3 is characterized in that, hydrogenation is 5 * 10
5Pa-70 * 10
5Carry out under the pressure between the Pa.
12. the method according to one of claim 1-3 is characterized in that, it per hour is that every gram catalyzer transforms 3 moles hydrogen at the most that the condition that reaction is carried out should make its productive rate.
13. the method according to claim 12 is characterized in that, it per hour is that every gram catalyzer transforms 2 moles hydrogen at the most that the condition that reaction is carried out should make its productive rate.
14. the method according to one of claim 1-3 is characterized in that, aromatic nitro compound is selected from and comprises at least two nitro functions and at least one C
6-C
14The unitary compound of aromatic series, above-mentioned aromatic series unit is by one or more C
1-C
10Straight chain, ring-type or side chain, saturated or undersaturated alkyl and/or one or more hydroxyl replace or do not replace.
15. according to the method for claim 14, wherein nitro-compound is selected from and comprises at least two nitro functions and at least one C
6-C
10The unitary compound of aromatic series.
16. the method according to one of claim 1-3 is characterized in that, hydrogenation is to carry out in the presence of the solvent of aromatic nitro compound being used for.
17. the method according to claim 16 is characterized in that, solvent is selected from Fatty Alcohol(C12-C14 and C12-C18) or cyclic ethers, they itself or their mixture.
18. the method according to claim 16 is characterized in that, the solvent that reaction is used is the aromatic amine product that the described aromatic nitro compound hydrogenation of claim 1 obtains.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0003903A FR2807036B1 (en) | 2000-03-28 | 2000-03-28 | CONTINUOUS HYDROGENATION OF AROMATIC NITER COMPOUNDS USING A LOW ALUMINUM CATALYST |
| FR0003903 | 2000-03-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1332148A CN1332148A (en) | 2002-01-23 |
| CN1198787C true CN1198787C (en) | 2005-04-27 |
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ID=8848566
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011178582A Expired - Lifetime CN1198787C (en) | 2000-03-28 | 2001-03-28 | Continuous hydrogenation process of aromatic nitro-compound using low content of aluminium catalyst |
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| Country | Link |
|---|---|
| US (1) | US6423872B2 (en) |
| EP (1) | EP1138665B1 (en) |
| JP (1) | JP2001316337A (en) |
| KR (1) | KR100784741B1 (en) |
| CN (1) | CN1198787C (en) |
| AT (1) | ATE249416T1 (en) |
| BR (1) | BR0101169B1 (en) |
| CA (1) | CA2342257C (en) |
| DE (1) | DE60100719T2 (en) |
| ES (1) | ES2202263T3 (en) |
| FR (1) | FR2807036B1 (en) |
| HU (1) | HU230415B1 (en) |
| ID (1) | ID29715A (en) |
| MX (1) | MXPA01003213A (en) |
| PL (1) | PL200746B1 (en) |
| PT (1) | PT1138665E (en) |
| SG (1) | SG91353A1 (en) |
| TW (1) | TW572872B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US8486223B2 (en) * | 2003-07-04 | 2013-07-16 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
| KR100612922B1 (en) | 2003-07-04 | 2006-08-14 | 농유 왕 | A process for producing 4-aminodiphenylamine |
| JP4546958B2 (en) | 2003-07-04 | 2010-09-22 | チアンス・シノケム・テクノロジー・カンパニー・リミテッド | Method for producing 4-aminodiphenylamine |
| KR100622711B1 (en) * | 2004-07-13 | 2006-09-14 | 현대자동차주식회사 | The anode of solid oxide fuel cell with networking structure and the preparing method of it |
| DE102005008613A1 (en) | 2005-02-23 | 2006-08-31 | Basf Ag | Preparation of e.g. aromatic amines comprises hydrogenating nitro-aromatic compounds in presence of catalyst, separating catalyst and measuring absorption of UV/visible radiation to determine concentrations of nitro and nitroso compounds |
| BRPI0721719A2 (en) * | 2007-05-29 | 2013-02-13 | Evonik Degussa Gmbh | activated metal based catalysts |
| WO2008145180A1 (en) * | 2007-05-29 | 2008-12-04 | Evonik Degussa Gmbh | Activated base metal catalysts |
| WO2008145179A1 (en) * | 2007-05-29 | 2008-12-04 | Evonik Degussa Gmbh | Activated base metal catalysts |
| JP5473923B2 (en) * | 2007-10-15 | 2014-04-16 | エボニック デグサ ゲーエムベーハー | High speed filtration powder catalyst mixture |
| CN102259029B (en) | 2010-05-24 | 2014-12-10 | 江苏圣奥化学科技有限公司 | Solid alkali catalyst |
| KR20130136502A (en) | 2010-12-06 | 2013-12-12 | 바스프 에스이 | Method for producing aromatic amines |
| US8981155B2 (en) | 2010-12-06 | 2015-03-17 | Basf Se | Process for preparing aromatic amines |
| CN103534230B (en) | 2011-03-16 | 2015-06-03 | 巴斯夫欧洲公司 | Optimized metering of reactants for a process for preparing aromatic amines by hydrogenation of nitroaromatics |
| US8835688B2 (en) | 2011-03-16 | 2014-09-16 | Basf Se | Optimized introduction of the starting materials for a process for preparing aromatic amines by hydrogenation of nitroaromatics |
| CN103747861B (en) * | 2011-06-24 | 2016-08-31 | 安格斯化学公司 | Use the method and apparatus being used for producing and filter amino alcohol of continuous stirred tank slurry reactor |
| CN110652985B (en) * | 2019-10-09 | 2022-05-10 | 南京科技职业学院 | Preparation method and application of catalyst for hydrogenation of dimer acid |
| CN112076745B (en) * | 2020-09-21 | 2023-03-03 | 中北大学 | High-efficiency palladium-carbon catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB821220A (en) * | 1957-06-27 | 1959-10-07 | Bayer Ag | A process for the production of toluylene diamines |
| FR1290268A (en) * | 1961-03-01 | 1962-04-13 | Derives De L Acetylene Soc Ind | Manufacturing process of toluylenediamines 2-4 and 2-6 |
| DE3537247A1 (en) * | 1985-10-19 | 1987-04-23 | Bayer Ag | USE OF MODIFIED RANEY CATALYSTS FOR PRODUCING AROMATIC DIAMINO COMPOUNDS |
-
2000
- 2000-03-28 FR FR0003903A patent/FR2807036B1/en not_active Expired - Lifetime
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2001
- 2001-03-27 KR KR1020010016066A patent/KR100784741B1/en not_active IP Right Cessation
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- 2001-03-27 CA CA002342257A patent/CA2342257C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JP2001316337A (en) | 2001-11-13 |
| BR0101169B1 (en) | 2011-05-03 |
| EP1138665B1 (en) | 2003-09-10 |
| CA2342257A1 (en) | 2001-09-28 |
| CN1332148A (en) | 2002-01-23 |
| PL346686A1 (en) | 2001-10-08 |
| KR20010093726A (en) | 2001-10-29 |
| HU230415B1 (en) | 2016-05-30 |
| PT1138665E (en) | 2003-12-31 |
| SG91353A1 (en) | 2002-09-17 |
| MXPA01003213A (en) | 2004-07-30 |
| EP1138665A1 (en) | 2001-10-04 |
| HUP0101198A3 (en) | 2002-12-28 |
| US6423872B2 (en) | 2002-07-23 |
| HUP0101198A2 (en) | 2002-08-28 |
| TW572872B (en) | 2004-01-21 |
| DE60100719D1 (en) | 2003-10-16 |
| US20010027257A1 (en) | 2001-10-04 |
| BR0101169A (en) | 2001-10-30 |
| ES2202263T3 (en) | 2004-04-01 |
| CA2342257C (en) | 2006-06-13 |
| ATE249416T1 (en) | 2003-09-15 |
| DE60100719T2 (en) | 2004-07-22 |
| FR2807036A1 (en) | 2001-10-05 |
| KR100784741B1 (en) | 2007-12-13 |
| FR2807036B1 (en) | 2002-05-10 |
| PL200746B1 (en) | 2009-02-27 |
| ID29715A (en) | 2001-10-04 |
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